Chemical ionization during the oxidation of methane and acetylene is experimentally and theoretically studied behind reflected shock waves over a wide temperature range and atmospheric pressure. The results of experimental measurements of the concentration of free electrons by microwave interferometry and electric probe method during the oxidation of acetylene and methane behind reflected shock waves are presented. A detailed kinetic model of the process of chemical ionization was developed. The results of experimental measurements and kinetic simulations are in good qualitative and quantitative agreement. The kinetic model of chemical ionization makes it possible to improve the kinetic description of the experimentally measured time histories of free electrons for the hydrocarbons studied.